Because they stand out from the rest of the list and get more attention. Also, they usually go at the end of the list, and people are most likely to notice the first and last items on a list.
As I understand it, the practice grew out of Jonathan Harris's situation on Lost in Space. He was added to the cast after the pilot, but all the other cast members' credit order was already set by contract, so he had to go last, but it would've been ignominious for an experienced adult actor to be billed after two children. So to compensate, they credited him as "Special Guest Star" for extra attention/prestige.
These days, it's become fairly standardized that an "And Actor as Character" credit at the end is second only to lead billing in prominence/pay. When Michael Shanks left Stargate SG-1 and later came back, they couldn't give him back his original second billing because it would mean demoting the other regulars, so instead they gave him an "And/as" credit at the end, which was pretty much comparable to second billing.
You can see a similar think in SG:A when Paul McGillion was added to the main cast in season 2 he got With/as credit along with David Hewlett who also got an and/as credit.